GB2272702A

GB2272702A - A process for the preparation of aluminium-heavy metal mixed complexes

Info

Publication number: GB2272702A
Application number: GB9323521A
Authority: GB
Inventors: Bansi Lal Kaul; Dominique Pflieger
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1992-11-19
Filing date: 1993-11-15
Publication date: 1994-05-25
Anticipated expiration: 2013-11-15
Also published as: GB9323521D0; FR2698096A1; GB2272702B; IT1262444B; US5698683A; CH686083A5; JPH06200174A; FR2698096B1; ITRM930763A0; ITRM930763A1

Abstract

A process for preparing a mixed aluminium-heavy metal dyestuff complex, in which the amount of heavy metal present is 10 - 98% and that of aluminium is 2 to 90%, characterized by i) reacting the metal free dyestuff with less than a stoichiometric amount of a heavy metal compound followed by ii) reacting the product with an aluminium compound in an amount to produce a stoichiometric excess of metal (calculated on all the metal present) to form a mixed aluminium-heavy metal complex.

Description

A PROCESS FOR THE PREPARATION OF ALUMINIUM-HEAVY METAL MIXED COMPLEXES When preparing heavy metal-dyestuff complexes, in order to ensure that complete metallisation has occurred and that no unreacted dyestuff remains (and so to avoid a worse final product), a stoicometric excess of metal is always added. Usually the stoicometric excess is in the order of 10-15%. This excess is however disadvantagous from the ecological point of view, since it produces 10-15% heavy metal salt which remains in the filtrate, after filtering the metal-dyestuff complexes. This filtrate therefore requires expensive processing before it is ecologically acceptable and can be safely discharged.

Further, problems arise with the heavy metal-dyestuff complexes themselves due to the toxicity of the metal that causes treatment, to make it ecologically safe, difficult. However, due to their effectiveness, particularly the chromium-, nickel-, cobalt- and copper-dyestuff complexes belong to the most important metal-dyestuff complexes available and people are not willing to do without them.

In order to reduce the amount of toxic residues in waste waters resulting from heavy metaldyestuff complexes, it has been found that mixed aluminium/heavy metal-dyestuff complexes are as effective as the heavy metal-dyestuff complexes without the toxicological drawbacks associated with the heavy metal-dyestuff complexes and by careful regulation of the preparation of these complexes, excess heavy metal salt can almost totally be eliminated.

To this end therefore, there is provided a process for preparing a mixed aluminium-heavy metal dyestuff complex in which the amount of heavy metal present is 10-98% and that of aluminium is 2 to 90%, characterised by i) reacting the metal free dyestuff with less than a stoicometric amount of a heavy metal compound followed by ii) reacting the product with an aluminium compound in an amount to produce a stoicometric excess of metal (calculated on all the metal present) to form a mixed aluminium-heavy metal complex.

The heavy metal of such complexes are preferably those that contain cobalt, copper, chromium and nickel.

Preferred chromium compounds used as a reactant in a process according to the invention are alkali dichromates.

Preferred cobalt compounds used as a reactant in a process according to the invention are cobalt salts such as cobalt chlorides and sulphates, especially CoSO4.7H2O, nitrates and acetates.

Preferred nickel and copper compounds used as a reactant in a process according to the invention are nickel and copper salts especially the halides, suphates or the acetates.

Preferably the amount of heavy metal compound used in a process according to the invention for a 1:1 complex is 10 to 98 mol % per mole of dyestuff and in 2:1 complexes 10 to 98 mol % per 2 mols of dyestuff.

Preferably the amount of aluminium used in a process according to the invention is 10 to 120 mol % of aluminium compound (with respect to the dyestuff). Preferably the aluminium compound used is aluminium sulphate.

Where chroming is carried out using alkali dichromate, a reducing compound such as sugar (e.g.

glucose), is to be added.

Further according to the invention there is provided a mixed aluminium-heavy metal complex in which the dyestuff is selected from any metal complex forming dyestuff, for example water soluble dyestuffs, solvent soluble dyestuffs and insoluble dyestuffs (i.e. pigments).

Preferred dyestuffs for use as a reactant in a process according to the invention are solvent soluble (i.e. water insoluble) dyestuffs.

Preferred complexes according to the invention are 2:1 azo- mixed aluminium-heavy metal complex dyes.

The properties of the complexes according to the invention compared to their aluminium-free counterparts are almost the same except in several cases for the nuances, which due to the aluminium content tend to be lightly hypsochrome.

Preferred complexes according to the invention are those of formula I and I'

in which each group R1 together with the two carbon atoms independently, to which R, is attached form a single ring or fused ring aromatic group, which is unsubstituted or further substituted by one to three groups selected from hydroxy, C,.4alkyl, C1-4alkoxy, cyano, nitro, rhodan, C1-4 alkylcarbonyl, benzoyl, C1.3alkylcarbonyloxy, aminocarbonyl, monoC1-4alkylaminocarbonyl, di (C1-4alkyl)aminocarbonyl, mono(C1-4alkoxy-C2-4alkyl)aminocarbonyl, di-(C1-4alkoxy-C2-4alkyl)aminocarbonyl, C1-3alkoxycarbonyl, aminosulphonyl, monoC1-4alkylaminosulphonyl, di(C1-4 alkyl)aminosulphonyl,mono(C1-4alkoxy-C2-4alkyl)aminosulphonyl,di(C1-4alkoxy-C2-4alkyl)aminosulphonyl and 4,6-bis-(bis(2',4'-dimethylphenyl) triazinyl-2; both groups R2, independently are selected from C3-20alkyl, C1.4alkoxy-C=.8alkyl and phenyl, which phenyl is unsubstituted or further substituted by one to three groups selected from hydroxy, C, 4 alkyl, C 1-4alkoxy, cyano, nitro, rhodan, C 4alkylcarbonyl, benzoyl, C 1-3alkylcarbonyloxy, aminocarbonyl, monoC1-4alkylaminocarbonyl, di(C1-4alkyl)aminocarbonyl, mono(C1-4alkoxy-C2-4 alkyl)aminocarbonyl, di(C1-4alkoxy-C2-4 lkyl)aminocarbonyl, C 3alkoxycarbonyl, aminosulphonyl, monoC1-4alkylaminosulphonyl, di(C1-4alkyl)aminosulphonyl, mono(C1-4alkoxy-C2-4alkyl)amino sulphonyl and di(C1-4alkoxy- C2-4alkyl)aminosulphonyl; each R1 and each R4 independently are selected from hydrogen, C,.4alkyl, C1-4alkoxy, cyano, nitro, C ,4alkoxycarbonyl, benzoyl, phenoxycarbonyl, aminocarbonyl, monoC 1.4al kyl- aminocarbonyl, di(C1-4alkyl)aminocarbonyl, mono (C .4alkoxy-C,4alkyl) aminocarbonyl, di(C1,4 al koxy-C2-4alkyl)aminocarbonyl. phenylaminocarbonyl, aminosulphonyl, monoC1 .4alkylamino- sulphonyl, di(CI 1-4alkyl)aminosulphonyl, mono(C 1.4alkoxy-C2.4alkyl) amino- suiphonyl, di(Cl al koxy-C,4 alkyl )aminosulphonyl and phenyl aminosulphonyl; Me is 10 to 98 mol % of a metal selected from chromium, copper, cobalt and nickel and 2 to 90 mol % aluminium; and X is a cation, Preferably R, is R,' where R,' together with the two carbon atoms to which it is attached forms a phenyl ring or a naphthyl ring as well as a heterocyclic aromatic ring, such as a five membered ring containing an oxygen, a sulphur and/or a nitrogen atom, (especially pyrazolone or pyridone).

Preferably in this Specification, any C1-4alkyl is preferably methyl or ethyl; any Alkoxy is preferably methoxy or ethoxy and preferably halogen is chlorine or bromine.

In the complexes of formula I, R, together with the two carbon atoms to which it is attached form a phenyl or 1-phenyl-3-methylpyrazolyl coupling component, in which the phenyl ring (of the phenyl or l-phenyl-3-methylpyrazolyl coupling component) is unsubstituted or substituted by 1 or 2 substituents selected from chloro, bromo,methyl, ethyl, methoxy, ethoxy, carbonamide and sulphonamide.

In the complexes of formula I', R, together with the two carbon atoms to which it is attached form a naphthyl or a phenyl ring, which naphthyl or phenyl ring is unsubstituted or substituted by I or 2 substituents selected from chloro, bromo,methyl, ethyl, methoxy, ethoxy, carbonamide and sulphonamide.

Preferably X' is X1+ where X'+ is selected from alkali metal ions, especially sodium, potassium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium, 4-amino-2,2,6,6tetramethylpiperidinyl, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl and 4-keto-2,2,6,6-tetramethylpiperidinyl ions. (Preferably the alkyl groups are C1-12 alkyl).

Preferred complexes of formula I and I' are selected from those of the formula Ia, Ib and Ic

in which each R3' independently is selected from nitro or -SO3NHR, where R7 is selected from hydrogen, C1-2 alkyl, C, 2 alkoxy-C2.3alkyl and phenyl; more preferably R, is R,' where R,' is methyl, ethyl, C1.2alkoxyC2.3alkyl or phenyl; each R6 is hydrogen, halogen, C1-2alkyl or C1.2alkoxy; more preferably R6 is R6' where R6' is selected from hydrogen,chloro and methyl, especially hydrogen; each R2' is 2-ethylhexyl or phenyl, unsubstituted or substituted by one to three substituents selected from chloro, bromo and methyl or one to two substituents selected from chloro, bromo and methyl, ethyl, C1-4alkoxy and acetyl; Me is 25 to 95 mol % Cr or Co and 5 to 75 mol % Al; X2 is selected from sodium, potassium, ammonium, C1-10alkylammonium, 4-amino-2,2,6,6tetramethylpiperidinyl, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl and 4-keto-2,2,6,6-tetramethylpiperidinyl ions and each R,f, and each R1, independently are selected from hydrogen, halogen, hydroxy, C, 4alkyl, C, 4 alkoxy, acetyl, benzoyl and 4,6-bis-(bis(2',4'-dimethylphenyl) triazinyl-2; or R", and R" in a particular phenyl ring together with the phenyl ring to which they are attached form a naphthyl group, preferably attached in the 5' and 6' position and whereby the substituents R3, are in the 4- or 5-position.

Preferably the metallisation of the metal-free dyestuffs can be carried out in alkali-aqueous medium, preferably at temperatures of 40-100"C more preferably at temperatures between 70950C. The pH values generally lie between 10 and 12. Advantageously, a solvent, such as a glycol or glycol ether can be added to the aqueous medium.

For chroming, for example dichromate is added to a well mixed suspension of the dyestuff and about twice the amount of a reducing agent, the mixture is mixed for three hours and then, always at temperatures up to 100 C, the aluminium salt, dissolved in water, is added.

The other salts (i.e. copper, nickel or cobalt containing salts can be treated in a similar fashion, without the need to add a reducing agent.

After salting out and washing the dissolved salt, the metal complex mixture can be isolated by known methods.

The mixed metal dyestuff complexes according to the invention can be used for the same uses as for the pure heavy metal dyestuff complexes of the prior art. The metal complex dyestuff mixtures according to the invention that are free of water solubilising groups are useful for dyeing (including dyeing in the mass) of plastics masses, including solvent free and solvent containing plastics masses or plastics resins. For example the metal complex dyestuff mixtures according to the invention can be applied in finishes having an oil or aqueous base, in various lacquers, in spin dyeing of viscose or cellulose acetate, for dyeing of natural and synthetic polyamide, polyester, polyolefins (such as polyethylene), polystyrene, polyvinylchloride, rubber and artificial leather.The metal complex dyestuff mixtures according to the invention can be used for printing of graphic material, for dyeing of paper masses, for coating of textile and leather or for printing uses.

Dyeings made from metal complex dyestuff mixtures according to the invention show excellent fastness to the effects of heat, have good light fastness and good weatherability, have good fastness to chemicals have good migration properties, good blooming properties, good overcoating finish properties, good solvent fastness properties, good dyeing strength and good application properties (e.g. good flocculation fastness etc).

Dyeing and printing can be carried out on the abovementioned materials by known methods.

For the avoidance of doubt, the term "mixed aluminium - heavy metal complexes" includes i) a mixture of an aluminium complex and a heavy metal complex, and ii) a single complex containing both heavy metal and aluminium In this specification an example of a single complex (i.e. of a complex of formula Ia) containing both heavy metal and aluminium is:

In a similar fashion a complex of formula Ib can be formed.

The invention will now be illustrated by the following Examples.

In the following Examples all parts are by weight and all percentages are by weight, unless indicated to the contrary. All temperatures are in "C. I part by volume equates to I part by volume of water.

Example 1 a) 51.3 parts of 1-amino-2-hydroxy-4-nitrobenzene are stirred into a solution of 250 parts water and 92.5 parts of 30% HCI. 100 parts of ice are then added and then the amine is diazotised with 83 parts by volume of a 4N NaNO2 solution. Buffering is carried out using sodium acetate to bring the mixture to a pH of 4.5. A solution of 56 parts of l-phenyl-3- methylpyrazolone-5 in 400 parts of water and 48 parts of 30% NaOH solution is then introduced slowly. By the simultaneous addition of 39 parts of 30% HC1 the pH value is maintained at 4.5 during coupling. The resultant suspension is stirred for 8 hours at room temperature and then stirred for half an hour at 80"C. The precipitate is then filtered, washed in 1500 parts of hot water and then dried.

b) 36.6 parts of the monoazo dyestuff of part a) above is suspended in 120 parts of water, 20 parts by volume of diethyleneglycol monomethylether and 33 parts of 30% NaOH. This is warmed to 70"C and stirred for 30 minutes. The pH of the suspension is about 11.9.

c) After heating to 95"C, a solution of 7.8 parts of cobalt sulphate (CoSO4.7H2O) in 50 parts of water is added over 30 minutes. After stirring for two hours at 95"C, a solution of I part aluminium sulphate in 2 parts of water is slowly added.

After stirring for 2 hours at 95"C, the dyestuff is filtered hot, washed with 1% NaCI solution until the filtrate is colourless and neutral and then is washed with about 300 parts of cold water to remove soluble inorganic salt.

The resultant dyestuff is of formula la

in which Me is 98% cobalt and 2% aluminium.

Example 2 The method of Example 1 parts a and b are repeated followed by: c) After warming to 95"C a solution of 7.8 parts of sodium dichromate and 16.3 parts of glucose in 50 parts of water is added over 30 minutes. This is stirred for 2 hours at 950C and I part of aluminium sulphate dissolved in 2 parts of water is added. The mixture is stirred for a further hour and a complex mixture of formula la in which Me is 98% chromium and 2% aluminium results.

Examples 3-9 By a method analogous to that of Example 1 or 2, compounds of the formula

in which the symbols are defined in Table I below can be prepared from appropriate reactants Table 1 Ex. No. R Ring B Me X'+ Nuance on dyeings

3 4-15-nitro X 92% Co, 8% Al Dicyclohexyl- black (mixed 1:1) ammonium 4 do. do. 92% Cr, 8% Al do. do.

5 5-SO2NH(CH2)3OCH3 do 87% Co, 13% Al sodium violet 6 do. do. 87% Cr, 13% Al do. do.

7. do. do. 50% Co, 50% Al do red 8. do. do. 50% Co, 50% Al 4-amino-2,2,6,6- red tetramethyl piperidimium 9 4-/5-nitro do 70% Cr, 30% Al 25% 2-ethyl- black hexylammonium 75% dicyclohexyl ammonium Examples 7-23 By a method analogous to that of Example 1 or 2, compounds of the formula

in which the symbols are defined in Table 2 below can be prepared from appropriate reactants.

Table 2 Ex. No. R R4 Me X1 Nuance of the dyeing

(C32N- ;jC2H5)2 red 10 4-nitro H 95% Co, 5% Al mN(C202 red II do. H 95% Cr, 5% Al do do 12 5-SONHCH3 3-C1 84% Co, 16% Al 25% 2-ethylhexylammonium orange 75% dicyclohexylammonium 13 do do 84% Cr, 16% Al do do 14 4-SO2NHCH3 do. 98% Co, 2% Al potassium scarlet 15 do do. 98% Cr, 2% Al do do 16 5-nitro H 98% Co, 2% Al sodium red 17 do. H 98% Cr, 2% Al do do 18 5-SO2NHCH3 Cl 25% Co, 75% Al do gold yellow 19 do H 25% Co, 75% Al 4-amino-2,2,6,6-tetramethyl- do piperidimium 20 4-SO.NHCH3 Cl 40% Cr, 60% Al do orange 21 4-nitro H 30% Co, 70% Al 4-keto-2,2,6,6-tetramethyl- goldyellow piperidimium 22 5-nitro H 70% Cr, 30% Al sodium orange 23 5-SO2NHCH3 Cl 75% C7, 25% Al do. do.

Examples 23-28 In the Examples of Table 3 below, the Me content is 80% Cobalt and 20% Aluminium.

Table 3 Ex. No. Dyestuff mixture Cation Nuance on the dyeing

24 yellow H3C(CH2)3- ICHNH QIr\5 HsC6-NH-S024 CH2--N=NN--FFi-CO \= < F-cy *-N 0 ,o o/ \o 9 0 C---NIN---S4NHC,Y ru I E H3C-(CF2)3-CHr 25 red COC6H5 HsCNHSO29 4 C4g h,, CH, .CS 0\ -0 6- position Me c ::Y 0 c in 4- or 6 position C006H5 SO2NHCS

26 yellow oCIr\a fyI-il OCH, CS $' vN=N9 CO *-Nvo Ou O CW CH3 Me N faC < -e FSN ocS red I CocS I cW CW E CH, i CH,o ss 3So2NHC6Hs cock OH

28 red ,coc,rS H3CNHSO2 > N )"OH in 4 or c113 O 0 6- position Me o//No Ho CI-il c in 4-or6- 42\1/\ position c C6H5 S4NH(CH3,0CH, Application Example 5 parts of the dyestuff of Example 1 (formula la) in a Dissolver apparatus are stirred into 95 parts of a nitrocellulose lacquer prepared from: : 18.8% of Nitrocellulose A15 (in the form of white flocs wetted with 35% isopropanol) 6.3% of an acrylic acid butyl ester polymer, a softener resin (Acronal 4F from BASF) 3.3% of diphenyloctylphosphate, a softener (Santiciser 141 from Monsanto) 10.0% of methoxy propanol (Dowanol PM from Dow Chemical) 10.0% ethoxypropanol 41.6% ethanol, and 10.0% ethyl acetate.

This is dissolved overnight in a rolling block. The solubility is very good.

With a 25Klm blade, a wet film of this lacquer composition is placed on aluminium foil and the lacquer is dried for 5 hours at 1300C. A orange-yellow lacquer coating results with good light and migration fastness properties.

The application example can be repeated using 5 parts of any one of the new dye complex of the invention of Examples 2-28 in place of that of Example 1.

Claims

Claims:

1. A process for preparing a mixed aluminium-heavy metal dyestuff complex in which the amount of heavy metal present is 10-98 mol% and that of aluminium is 2 to 90 mol%, characterized by i) reacting the metal free dyestuff with less than a stoichiometric amount of a heavy metal compound followed by ii) reacting the product with an aluminium compound in an amount to produce a stoichiometric excess of metal (calculated on all the metal present) to form a mixed aluminium-heavy metal complex.

2. A process according to Claim 1 in which the heavy metal of the complexes are those that contain cobalt, copper, chromium and nickel.

3. A process according to Claim 2 in which a) the chromium compounds used as a reactant are selected from alkali dichromates; b) the cobalt compounds used as a reactant are selected from cobalt chlorides and sulphates c) the nickel and copper compounds used as a reactant are selected from nickel and copper halides, sulphates or the acetates; and d) the aluminium compound used is aluminium sulphate.

4. A process according to any one of the preceding claims in which the amount of heavy metal compound used in a process according to the invention for a 1:1 complex is 10 to 98 mol % per mole of dyestuff and in 2:1 complexes 10 to 98 mol % per 2 mols of dyestuff.

5. A process according to any one of the preceding claims in which the amount of aluminium used in a process according to the invention is 10 to 120 mol % of aluminium compound (with respect to the dyestuff).

6. A process according to any one of the preceding claims in which in the mixed aluminium-heavy metal complex in which the dyestuff is selected from water soluble dyestuffs, solvent soluble dyestuffs and insoluble dyestuffs and pigments.

7. A process according to Claim 6 in which the dyestuff used is a solvent soluble (i.e.

water insoluble) dyestuffs.

8. A process according to any one of the preceding claims in which the complex is a 2:1 azo- mixed aluminium-heavy metal- complex dye.

9. A process according to Claim 1 in which the complex is one of formula I and I'

in which each group R1 together with the two carbon atoms independently, to which R1 is attached form a single ring or fused ring aromatic group, which is unsubstituted or further substituted by one to three groups selected from hydroxy, C1-4alkyl, C1-4alkoxy, cyano, nitro, rhodan, C1-4 alkylcarbonyl, benzoyl, C1-3alkylcarbonyloxy, aminocarbonyl, monoC1-4alkylaminocarbonyl, di-(C1-4alkyl)aminocarbonyl, mono(C1-4alkoxy-C2-4alkyl)amino-carbonyl, di-(C1-4alkoxy-C2-4alkyl)-aminocarbonyl, C1.3alkoxycarbonyl, aminosulphonyl,monoC1-4alkylaminosulphonyl,di(C1-4alkyl)aminosulphonyl,mono(C1-4alkoxy C2-4alkyl)-aminosulphonyl,di(C1-4alkoxy-C2-4alkyl)amino-sulphonyland4,6-bis-(bis(2',4'dimethyl-phenyl) triazinyl-2;; both groups R2, independently are selected from C3.20alkyl, C1 4alkoxy-C2.8alkyl and phenyl, which phenyl is unsubstituted or further substituted by one to three groups selected from hydroxy, C1-4alkyl, C1-4alkoxy, cyano, nitro, rhodan, Cl4alkylcarbonyl, benzoyl, C1-3alkyl-carbonyloxy, aminocarbonyl, monoC1-4alkylaminocarbonyl, di(C1-4 alkyl)aminocarbonyl,mono(C1-4alkoxy-C2-4alkyl)aminocarbonyl,di(C1-4alkoxy-C2-4alkyl)aminocarbonyl, C13 alkoxycarbonyl, aminosulphonyl, monoC1-4alkylaminosulphonyl, di(C1-4alkyl)amino-sulphonyl, mono(C1-4alkoxy-C2-4alkyl)amino-sulphonyl and di(C1-4 alkoxy-C24aIkyl)amino- sulphonyl;; each R3 and each R4 independently are selected from hydrogen, C1-4alkyl, C14alkoxy, cyano, nitro, C1-4alkoxycarbonyl, benzoyl, phenoxycarbonyl, aminocarbonyl, mono C1-4alkylaminocarbonyl, di(C1-4alkyl)aminocarbonyl, mono (C1-4alkoxy-C2-4alkyl) aminocarbonyl, di(C1-4alkoxy-C2-4alkyl)aminocarbonyl, phenylaminocarbonyl, amino sulphonyl, monoC1-4alkylamino-sulphonyl, di(C1-4alkyl)aminosulphonyl, mono(C1-4 alkoxy-C2-4alkyl)aminosulphonyl, di(C1-4alkoxy-C2-4alkyl)aminosulphonyl and phenyl aminosulphonyl; Me is 10 to 98 mol % of a metal selected from chromium, copper, cobalt and nickel and 20 to 90 mol % aluminium; and X+ is a cation.

10. A process according to Claim 1 in which the complex is one of formula Ia, Ib or Ic

in which each R3' independently is selected from nitro or -SO3NHR7, where R7 is selected from hydrogen, C1-2 alkyl, C1-2 alkoxy-C2-3alkyl and phenyl; each R6 is hydrogen, halogen, C1-2alkyl or Cl.2alkoxy; each R2, is 2-ethylhexyl or phenyl, unsubstituted or substituted by one to three substituents selected from chloro, bromo and methyl or one to two substituents selected from chloro, bromo and methyl, ethyl, C1-4alkoxy and acetyl; Me is 25 to 95 mol % Cr or Co and 5 to 75 mol % Al;; X2+ is selected from sodium, potassium, ammonium, C1.10aikylammonium, 4-amino 2,2,6,6-tetramethylpiperidinyl, 4-hydroxy-2,2,6 ,6-tetramethylpiperidinyl and 4-keto 2,2,6 ,6-tetra-methylpiperidinyl ions and each Rlo and each R11 independently are selected from hydrogen, halogen, hydroxy, C1-4 alkyl, C1-4 alkoxy, acetyl, benzoyl and 4,6-bis-(bis(2',4'-dimethylphenyl) triazinyl-2; or Rlo and R11 in a particular phenyl ring together with the phenyl ring to which they are attached form a naphthyl group, preferably attached in the 5' and 6' position and whereby the substituents R3, are in the 4- or 5-position.

11. A mixed aluminium-heavy metal dyestuff complex in which the amount of heavy metal present is 10-98 mol% and that of aluminium is 2 to 90 mol%.

12. A complex according to Claim 11 in which the heavy metal of the complexes are those that contain cobalt, copper, chromium and nickel.

13. A complex formula I and I'

in which each group R1 together with the two carbon atoms independently, to which R1 is attached form a single ring or fused ring aromatic group, which is unsubstituted or further substituted by one to three groups selected from hydroxy, C1-4alkyl, Cl4alkoxy, cyano, nitro, rhodan, C1-4 alkylcarbonyl, benzoyl, C1 .3alkylcarbonyloxy, aminocarbonyl, mono 4 alkylaminocarbonyl, di-(C1-4alkyl)aminocarbonyl, mono(CI4alkoxy-C24alkyl)- aminocarbonyl, di-(C1-4alkoxy-C2-4alkyl)-aminocarbonyl, C1-3alkoxycarbonyl, aminosulphonyl,monoC1-4alkylaminosulphonyl,di(C1-4alkyl)aminosulphonyl, mono(C1-4 alkoxy-C2-4alkyl)-aminosulphonyl, di(C1-4alkoxy-C2-4alkyl)amino-sulphonyl and 4,6-bis (bis(2',4'-dimethyl-phenyl)triazinyl-2; both groups R2, independently are selected from C3.20alkyl, C1-4alkoxy-C2-8alkyl and phenyl, which phenyl is unsubstituted or further substituted by one to three groups selected from hydroxy, C1-4 alkyl, Cl4alkoxy, cyano, nitro, rhodan, Cl4alkylcarbonyl, benzoyl, C1-3 alkylcarbonyloxy, aminocarbonyl, monoC1-4alkylaminocarbonyl, di(C1-4 alkyl)aminocarbonyl,mono(C1-4alkoxy-C2-4alkyl)aminocarbonyl,di(C1-4alkoxy-C2-4alkyl)aminocarbonyl, C1.3 alkoxycarbonyl, aminosulphonyl, monoC1-4alkylaminosulphonyl, di(C1-4alkyl)-aminosulphonyl, mono(C1-4alkoxy-C2-4alkyl)amino-sulphonyl and di(C1-4 alkoxy-C2-4alkyl)-aminosulphonyl; each R3 and each R4 independently are selected from hydrogen, C1.4alkyl, Cl.4alkoxy, cyano, nitro, C1-4alkoxycarbonyl, benzoyl, phenoxycarbonyl, aminocarbonyl, monoC1-4 alkylaminocarbonyl, di(C1-4alkyl)aminocarbonyl, mono(C1-4alkoxy-C2-4alkyl) aminocarbonyl, di(C1-4 alkoxy-C2-4alkyl)aminocarbonyl, phenylaminocarbonyl, aminosulphonyl, monoC1-4alkylamino-sulphonyl, di(C1-4alkyl)aminosulphonyl, mono (C1-4alkoxy-C2-4alkyl) amino- sulphonyl, di(C1-4alkoxy-C2-4alkyl)aminosulphonyl and phenylaminosulphonyl; Me is 10 to 98 mol % of a metal selected from chromium, copper, cobalt and nickel and 2 to 90 mol % aluminium; and X+ is a cation.

14. A complex of formula Ia, Ib or Ic

in which each R3, independently is selected from nitro or -SO3NHR7, where R, is selected from hydrogen, C12 alkyl, C1.2 alkoxy-C2.3alkyl and phenyl; each R6 is hydrogen, halogen, C1-2alkyl or C1-2alkoxy; each R2, is 2-ethylhexyl or phenyl, unsubstituted or substituted by one to three substituents selected from chloro, bromo and methyl or one to two substituents selected from chloro, bromo and methyl, ethyl, C1-4alkoxy and acetyl; Me is 25 to 95 mol % Cr or Co and 5 to 75 mol % Al; X2+ is selected from sodium, potassium, ammonium, C1-10alkylammonium, 4-amino2,2,6,6-tetramethylpiperidinyl, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl and 4-keto2,2,6,6-tetramethyl-piperidinyl ions and each R10 and each R11 independently are selected from hydrogen, halogen, hydroxy, C1.

4alkyl, C1-4 alkoxy, acetyl, benzoyl and 4,6-bis-(bis (2',4'-dimethylphenyl) triazinyl-2; or Rlo and Rl, in a particular phenyl ring together with the phenyl ring to which they are attached form a naphthyl group, preferably attached in the 5' and 6' position and whereby the substituents R3, are in the 4- or 5-position.

15. A process for the preparation of a mixed aluminium-chromium dyestuff complex having a chromium content stoichometrically, of 80 to 98% and an aluminium content of 2 to 20% characterized in that chroming of the metal-free dyestuff is carried out with less than a stoichiometric amount of an alkali dichromate and a reducing organic compound and sufficient aluminium compound that an stoichiometric excess of metal, when aluminium and chromium are calculated together, results.

16. A complex having a chromium content stoichometrically, of 80 to 98% and an aluminium content of 2 to 20%.

17. A process for the preparation of a mixed aluminium-cobalt dyestuff complex having a chromium content stoichometrically, of 25 to 98% and an aluminium content of 2 to 75% characterized in that the reaction of the metal-free dyestuff is carried out with less than a stoichiometric amount of a cobalt compound and with a sufficient amount of aluminium compound that an stoichiometric excess of metal, when aluminium and cobalt are calculated together results.

18. A complex having a chromium content stoichometrically, of 25 to 98% and an aluminium content of 2 to 75%.